U.S. patent number 5,688,902 [Application Number 08/672,163] was granted by the patent office on 1997-11-18 for process for the preparation of polyimides or of their biodegradable polypeptide hydrolysates.
This patent grant is currently assigned to Rhone-Poulenc Chimie. Invention is credited to Jean-Marie Bernard, Jean-Luc LePage, Arnaud Ponce, Florence Tournilhac.
United States Patent |
5,688,902 |
Bernard , et al. |
November 18, 1997 |
Process for the preparation of polyimides or of their biodegradable
polypeptide hydrolysates
Abstract
Process for the preparation of polyimides or of their
polypeptide hydrolysates which are at least 80% biodegradable, by
thermal polycondensation of at least one amino acid, optionally
followed by hydrolysis, the thermal polycondensation step being
carried out in the presence of at least one "acid catalyst" chosen
from sulphuric, nitric, phosphorous, sulphurous, hydrofluoric,
silicic and sulphonic acids, organic sulphonic acids containing
less than 50 carbon atoms, amino acids bearing a non-carboxyl
strong acid function, organic phosphonic acids, organic carboxylic
acids having a pK.sub.a lower than or equal to 5, preferably lower
than or equal to 3; precursors of these acids; salts of these acids
and of an amino acid which is similar to or different from that or
those used; salts of these acids and of a polyimide derived from
the polycondensation of at least one amino acid which is similar to
or different from that or those used; hydrochloric acid and its
precursors salts of hydrochloric acid and of an amino acid which is
similar to or different from that or those used, when the amino
acid to be polycondensed is other than glutamic acid; salts of
hydrochloric acid and of a polyimide derived from the
polycondensation of at least one amino acid which is similar to or
different from that or those used; acid salts of sulphuric,
phosphoric or phosphorous acids or their precursors; phosphoric
acid precursors other than phosphoric anhydride or polyphosphoric
acids; and Lewis acids; according to an "acid catalyst"/amino acid
molar ratio of at least 0.001. Use of the polyimides or of the
polypeptide hydrolysates thus obtained in detergent compositions,
and detergent compositions containing the said polyimides or
hydrolysates.
Inventors: |
Bernard; Jean-Marie (Mornant,
FR), LePage; Jean-Luc (Francheville, FR),
Ponce; Arnaud (Aubervilliers, FR), Tournilhac;
Florence (Paris, FR) |
Assignee: |
Rhone-Poulenc Chimie
(Courbevoie, FR)
|
Family
ID: |
26230752 |
Appl.
No.: |
08/672,163 |
Filed: |
June 27, 1996 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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342943 |
Nov 21, 1994 |
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Foreign Application Priority Data
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Nov 24, 1993 [FR] |
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93 14042 |
Nov 24, 1993 [FR] |
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93 14043 |
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Current U.S.
Class: |
528/313; 528/312;
528/322; 524/706; 524/742; 524/745; 524/730; 528/499; 528/318;
528/314; 528/315 |
Current CPC
Class: |
C08G
73/1092 (20130101); C08G 73/1028 (20130101); C11D
3/3719 (20130101); C08G 69/10 (20130101); C08G
73/0611 (20130101); C08G 73/1021 (20130101) |
Current International
Class: |
C08G
73/10 (20060101); C11D 3/37 (20060101); C08G
73/00 (20060101); C08G 069/08 (); C08G 073/10 ();
C08K 003/32 () |
Field of
Search: |
;528/312,313,314,315,318,322,499 ;524/706,730,742,745
;252/89.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2059475 |
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Jul 1970 |
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FR |
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0130935A1 |
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Apr 1984 |
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FR |
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WO87/03891 |
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Jul 1987 |
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FR |
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0454126A1 |
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Apr 1991 |
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FR |
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0511037A1 |
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Mar 1992 |
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FR |
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2461350 |
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Dec 1971 |
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DE |
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2246786 |
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Feb 1992 |
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GB |
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Other References
Journal of Medicinal Chemistry (Neri et al.), vol. 18, No. 8, pp.
893-897, Aug. 1973. .
French Preliminary Search Report #FR9314043. .
French Preliminary Search Report #FR9314042..
|
Primary Examiner: Acquah; Samuel A.
Attorney, Agent or Firm: Wood; John Daniel
Parent Case Text
This application is a continuation of application Ser. No.
08/342,943 filed Nov. 21, 1994, which application is now abandoned.
Claims
We claim:
1. A process for the preparation of polyimides or their polypeptide
hydrolysates which are at least 80% biodegradable, by thermal
polycondensation of at least one amino acid, optionally followed by
hydrolysis, the process comprising carrying out the thermal
polycondensation step in the presence of at least one "acid
catalyst" selected from the group consisting of
a) sulfuric, nitric, phosphorus, sulfurous, hydrofluoric, silicic
and sulphonic acids, organic sulphonic acids, containing less than
50 carbon atoms, amino acids bearing a non-carboxyl strong acid
function, organic phosphonic acids, organic carboxylic acids having
a pK.sub.a lower than or equal to 5;
b) precursors of these acids;
c) salts of the acids of step a)with an amino acid which is similar
to or different from that or those used;
d) salts of the acids of step a) with a polyimide derived from the
polycondensation of at least one amino acid which is similar to or
different from that or those used;
e) hydrochloric acid and its precursors
f) hydrochloric acid salts of an amino acid which is similar to or
different from that or those used, when the amino acid to be
polycondensed is other than glutamic acid;
g) hydrochloric acid salts of a polyimide derived from the
polycondensation of at least one amino acid which is similar to or
different from that or those used;
h) acid salts of sulfuric, phosphoric or phosphorous acids or their
precursors;
i) phosphoric acid precursors other than phosphoric anhydride or
polyphosphoric acids; and
j) Lewis acids;
according to an "acid catalyst"/amino acid molar ratio of at least
0.001; said thermal polycondensation operation being carried out in
bulk, with a reaction medium remaining in the pulverulent or
friable form throughout the whole of the polycondensation
operation, in which reaction medium the "acid catalyst" is
distributed homogeneously.
2. A process according to claim 1, wherein the "acid catalyst"
is
a) methanesulphonic, benzenesulphonic, trifluoromethanesulphonic,
dodecylbenzenesulphonic, para-toulenesulphonic or cysteic acid;
b) anhydrous or hydrated sulfuric acid, oleum, acid sulfates of
potassium, lithium, sodium or quaternary ammonium, SO.sub.3 ;
c) ammonium sulfate;
d) neutral alkali metal sulfate/sulfuric acid or neutral alkali
metal or alkaline-earth metal sulfate/phosphoric or pyrophosphoric
acid mixtures, according to an acid/neutral salt molar ratio of the
order of 0.5/1 to 10/1;
e) hydrogen phosphate of potassium, sodium, lithium or quaternary
ammonium;
f) HCl, PCl.sub.3, PCl.sub.5, POCl.sub.3, cyanuric chloride;
g) SiCl.sub.4, CH.sub.3 SiCl.sub.3 ;
h) salicylic acid, chloroacetic acids, and the like;
i) phosphomethylglycine, ethylphosphonic acid;
j) aspartic acid hydrochloride, salts of aspartic acid with
sulfuric, methanesulphonic and para-toulenesulphonic acids;
k) polyanhydroaspartic acid hydrochloride; and
l) AlCl.sub.3, BF.sub.3, ZnCl.sub.2.
3. A process according to claim 1, wherein the amino acid used is
aspartic acid or glutamic acid taken alone or mixed together or
with another amino acid.
4. A process according to claim 1, wherein the thermal
polycondensation operation is carried out at a temperature of the
order of 100.degree. to 250.degree. C.
5. A process according to claim 1, wherein the thermal
polycondensation operation is carried out in bulk or in a solvent
medium.
6. A process according to claim 1, wherein an acid salt of an amino
acid salt is used as sole constituent of the reaction in place of
an amino acid/"acid catalyst" mixture.
7. A process according to claim 1 further characterized in that the
"acid catalyst" is distributed homogeneously in the reaction medium
by a step selected from the group consisting of
a) forming a paste of a mixture of amino acid and of solid or
liquid "acid catalyst" with water or other volatile liquid diluent
by evaporation under vacuum or at atmospheric pressure and then
grinding the mass obtained;
b) dissolving the amino acid and solid or liquid "acid catalyst" in
water or other dissolver of the amino acid and of the catalyst and
then atomizing the solution;
c) atomizing a suspension of amino acid in a solution of solid or
liquid "acid catalyst" in water or other dissolver of the
catalyst;
d) evaporating a solution of solid or liquid "acid catalyst" in
water or other dissolver of the catalyst on a fluidized bed of
amino acid; and
e) cogrinding or micronizing a mixture of amino acid and solid
"acid catalyst".
8. A process according to claim 1 wherein the "acid catalyst"/amino
acid molar ration is of the order of 0.001 to 0.15, when the "acid
catalyst" consists of an acid salt or of an acid salt precursor,
and of the order of 0.001 to 0.05, when the "acid catalyst" is
other than an acid salt or an acid salt precursor.
9. A process according to claim 1, wherein the polyimide obtained
by thermal condensation is hydrolyzed to a polypeptidic salt by
addition of a basic agent, the said salt optionally being
subsequently neutralized to a polypeptidic acid by addition of an
inorganic or organic acid.
10. An aqueous detergent solution containing a detergent
composition comprising a polyimide which has a charge density
COO.sup.- ranging from 0 to 5.times.10.sup.-4 mol/g of polymer and
which is capable of acquiring in the aqueous solution a charge
density COO.sup.- at least equal to 10.sup.-3 mol/g of polymer or a
polypeptide hydrolysate of the said polyimide, said polyimide or
its polypeptide hydrolysate being obtained according to the process
which forms the subject of claim 1.
11. An aqueous detergent solution according to claim 10, wherein
the polyimide or its polypeptide hydrolysate represents of the
order of 0.2 to 80%, of the weight of the said detergent
solution.
12. A detergent composition containing the polyimides or their
polypeptide hydrolysate obtained according to the process of claim
1.
13. A process according to claim 1, wherein said organic sulphonic
acids contain less than 25 carbons.
14. A process according to claim 1, wherein said organic carboxylic
acid of step a) has a pK.sub.a lower than or equal to 3.
15. A process according to claim 1, wherein the "acid
catalyst"/amino acid molar ratio is of the order of 0.005 to
10.
16. A process according to claim 1, wherein the "acid
catalyst"/amino acid molar ration is of the order of 0.01 to 5.
17. A process according to claim 2, wherein the acid neutral salt
molar ratio is of the order of 1/1 to 3/1.
18. A process according to claim 8, wherein said "acid
catalyst"/amino acid molar ration is of the order of 0.005 to 0.15
when the "acid catalyst" consists of an acid salt or of an acid
salt precursor.
19. A process according to claim 8, wherein said "acid
catalyst"/amino acid molar ratio is of the order of 0.005 to 0.05
when the "acid catalyst" is other than an acid salt or an acid salt
precursor.
20. An aqueous detergent solution according to claim 11 wherein the
polyimide or its polypeptide hydrolysate represents of the order of
2 to 50%.
Description
The subject of the present invention is a process for the
preparation of polyamides, in particular polysuccinimides, or of
their polypeptide hydrolysates which are naturally at least 80%
biodegradable. It also concerns the use of the polyamides or of the
polypeptide hydrolysates thus obtained in detergent compositions,
as well as detergent compositions containing the said polyamides or
their hydrolysates as "builder" or "cobuilder" agents.
It is known to obtain polyimides by thermal polycondensation of
amino acids, especially aspartic acid, for which the polypeptide
hydrolysates have a biodegradability in natural medium of the order
of 75% (EP-A-511037).
The Applicant has now found a process making it possible to obtain
polyimides, especially polyimides derived from aspartic acid, for
which the polypeptide hydrolysates are at least 80% and preferably
at least 85% biodegradable.
According to the invention it is a process for the preparation of
polyimides or of their polypeptide hydrolysates of at least 80%,
preferably of at least 85%, biodegradability, by thermal
polycondensation of at least one amino acid, optionally followed by
hydrolysis, the said process being characterized in that the
thermal polycondensation step is carried out in the presence of at
least one "acid catalyst" chosen from
sulphuric, nitric, phosphorous, sulphurous, hydrofluoric, silicic
and sulphonic acids, organic sulphonic acids containing less than
50 carbon atoms, preferably less than 25 carbon atoms, amino acids
bearing a non-carboxyl strong acid function, organic phosphonic
acids, organic carboxylic acids having a pK.sub.a lower than or
equal to 5, preferably lower than or equal to 3;
precursors of these acids;
salts of these acids and of an amino acid which is similar to or
different from that or those used;
salts of these acids and of a polyimide derived from the
polycondensation of at least one amino acid which is similar to or
different from that or those used;
hydrochloric acid and its precursors
salts of hydrochloric acid and of an amino acid which is similar to
or different from that or those used, when the amino acid to be
polycondensed is other than glutamic acid;
salts of hydrochloric acid and of a polyimide derived from the
polycondensation of at least one amino acid which is similar to or
different from that or those used;
acid salts of sulphuric, phosphoric or phosphorous acids or their
precursors;
phosphoric acid precursors other then phosphoric anhydride or
polyphosphoric acids;
and Lewis acids;
according to an "acid catalyst"/amino acid molar ratio of at least
0.001, preferably of the order of 0.005 to 10 and very particularly
of the order of 0.01 to 5.
Acid or acid salt precursor is understood to refer to any product
which liberates at least one of the abovementioned acids or acid
salts under polycondensation operating conditions; this liberation
may be obtained by virtue of the temperature or by the action of
the water formed in situ.
In the definition of the mole of "acid catalyst", elemental entity
will be taken as referring to protons in the case of acids, acid
salts or their precursors; in the case of a salt of an amino acid
or a polyimide, the elemental entity considered will be the
NH.sup.3+ function; in the case of Lewis acids the elemental entity
considered will be the molecule.
In the definition of the mole of amino acid, elemental entity will
be taken as referring to the molecule.
"Acids" will be understood hereinafter to refer to acids, acid or
acid salt precursors, Lewis acids and acid salts which are not
derived from amino acids mentioned above as catalysts; "amino acid
salts" or "aspartic acid salts" will be understood to refer to the
salts derived from inorganic or organic acids and from amino acids
or from aspartic acid; "polyimide salts" will be understood to
refer to the salts derived from inorganic or organic acids and from
a polyimide derived from the amino acid polycondensation.
Among the amino acids which my be used in order to carry out the
process of the invention, there may be mentioned aspartic acid or
glutmmic acid, taken alone or mixed together in any particular
proportions or mixed with another amino acid (for example up to 15%
by weight, preferably less than 5% by weight, of glycine, alanine,
valine, leucine, isoleucine, phenylalanine, methionine, histidine,
proline, lysine, serine, threonine, cysteine, etc.).
Aspartic acid is the preferred amino acid. When an "amino acid
salt" is used, this is preferably an "aspartic acid salt".
Among the "acid catalysts" which may be used, there may be
mentioned
sulphonic acids such as methanesulphonic, benzenesulphonic,
trifluoromethanesulphonic, dodecylbenzenesulphonic,
para-toluenesulphonic, cysteic acid (amino acid bearing a sulphonic
function), etc.
anhydrous or hydrated sulphuric acid, oleum, acid sulphates of
potassium, lithium, sodium or quaternary ammonium, SO.sub.3,
etc.
ammonium sulphate
neutral alkali metal sulphate/sulphuric acid or neutral alkali
metal or alkaline-earth metal sulphate/phosphoric or pyrophosphoric
acid mixtures, according to an acid/neutral salt molar ratio of the
order of 0.5/1 to 10/1, preferably of the order of 1/1 to 3/1
hydrogen phosphates of potassium, sodium, lithium or quaternary
ammonium, etc.
HCl, PCl.sub.3, PCl.sub.5, POCl.sub.3, cyanuric chloride
halosilanes such as SiCl.sub.4, CH.sub.3 SiCl.sub.3, etc.
salicylic acid, chloroacetic acids, etc.
phosphonic acids such as phosphomethylglycine, ethylphosphonic
acid, etc.
aspartic acid hydrochloride (when the amino acid to be
polycondensed is other than glutamic acid), salts of aspartic acid
and of sulphuric, methanesulphonic, para-toluenesulphonic etc.
acid
polysuccinimide hydrochloride (polyhydroaspartic acid
hydrochloride), etc.
AlCl.sub.3, BF.sub.3, ZnCl.sub.2.
The thermal polycondensation operation my be carried out at a
temperature of the order of 100.degree. to 250.degree. C.,
preferably at a temperature of the order of 150.degree. to
220.degree. C. The said operation my be carried out at a chosen
temperature, or one which follows a pre-established temperature
profile.
This thermal polycondensation operation my be carried out in bulk
or in a solvent medium, at atmospheric pressure, under pressure
(preferably up to 20 bars) or under vacuum (preferably greater than
1 mbar).
A bulk operation may thus be carried out, for example:
from the amino acid to which is added the "acid", the "amino acid
salt" or the "polyimide salt"; the "acid", the "amino acid salt" or
the "polyimide salt" may be introduced under hot or cold
conditions, at atmospheric pressure or under pressure, and in the
solid or liquid state;
from the amino acid with throughput of the "acid" in the gaseous
form, optionally diluted in an inert gas, if the said "acid
catalyst" is sufficiently volatile at the polycondensation
temperature.
The thermal polycondensation operation may also be carried out in a
solvent medium, for example:
from the amino acid suspended in a solvent, to which is added the
"acid", the "amino acid salt" or the "polyimide salt"; the "acid",
the "amino acid salt" or the "polyimide salt" may be introduced
under hot or cold conditions, at atmospheric pressure or under
pressure, and in the solid, liquid or gaseous form (optionally
diluted in an inert gas);
from the "acid", the "amino acid salt" or the "polyimide salt"
suspended or dissolved in a solvent, to which is added the amino
acid.
Among the solvents which my be used, there may be mentioned those
which are inert towards the "acid catalyst" and for which the
boiling point is greater than or equal to the reaction temperature,
such as dibutyl phthalate, diphenyl ether, decalin, tetralin,
ortho-cresol, etc.
A production variant of the thermal polycondensation operation in
bulk or in a solvent medium consists in using an "amino acid salt"
as the sole constituent of the reaction in place of an amino
acid/"acid catalyst" mixture; the said "amino acid salt" is thus
present in bulk or suspended in a solvent.
It is very particularly advantageous to carry out the
polycondensation operation in bulk with a reaction medium which
remains in the pulverulent or friable form throughout the whole of
the said operation. The polycondensation operation may then be
carried out industrially using a simple apparatus, and without
solidification of the medium, in the presence of a relatively low
amount of solid or liquid "acid catalyst". A means of avoiding
obtaining low levels of conversion of the amino acid, due to the
limited level of "acid catalyst" used, consists in distributing the
catalyst homogeneously in the pulverulent medium which is subjected
to the polycondensation operation. The amount of catalyst which may
be used depends on the nature of the said catalyst. Thus, when the
"acid catalyst" consists of an acid salt or of an acid salt
precursor, an "acid catalyst"/amino acid molar ratio of the order
of 0.001 to 0.15, preferably of the order of 0.005 to 0.15, is well
suited; when the "acid catalyst" is other than an acid salt or an
acid salt precursor, an "acid catalyst"/amino acid molar ratio of
the order of 0.001 to 0.05, preferably of the order of 0.005 to
0.05, is suitable.
There may be mentioned, among possible implementational modes which
make it possible to distribute the catalyst in the pulverulent
medium, the following:
forming a paste of a mixture of amino acid and of solid or liquid
"acid catalyst" with water (or any other volatile liquid diluant),
removing the water (or the diluent) by evaporation under vacuum or
at atmospheric pressure and then grinding the mass obtained;
dissolving the amino acid and solid or liquid "acid catalyst" in
water (or in any other dissolver of the amino acid and of the
catalyst), preferably while hot, and then atomizing the
solution;
atomizing a suspension of amino acid in a solution of solid or
liquid "acid catalyst" in water (or in any other dissolver of the
catalyst);
evaporating a solution of solid or liquid "acid catalyst" in water
(or in any other dissolver of the catalyst) on a fluidized bed of
amino acid;
cogrinding or micronizing a mixture of amino acid and of solid
"acid catalyst";
preparation of aspartic acid especially, by reaction of an organic
or inorganic acid and of ammonium aspartate, with incorporation, by
crystallization, of the solid "acid catalyst" during the operation
of precipitation of the aspartic acid.
The polyimide obtained according to the process of the invention
may, if necessary, be separated, filtered, purified and dried.
Depending on the nature of the "acid catalyst" and of the medium,
the catalyst may, if necessary, be separated from the polyimide by
washing with water or with the aid of a solvent for the said "acid
catalyst" which is not a solvent for the polyimide.
The polyimide may be purified by dissolution with the aid of a
polar aprotic solvent (dimethylformamide, formamide, dimethyl
sulphoxide, etc.) followed by reprecipitation with the aid of a
compound which is not a solvent for the said polyimide (water,
ether, ethanol, acetone, etc.).
The polyimide obtained, which is separated out or otherwise, may
subsequently be hydrolysed, preferably by addition of a basic agent
(alkali metal base, alkaline-earth metal base, alkali metal
carbonate or alkaline-earth metal carbonate, etc.) if necessary in
the presence of water, and in a homogeneous or two-phase medium; in
the case of the polysuccinimide derived from aspartic acid, the
hydrolysate thus obtained consists of polyaspartate (of sodium for
example).
The acid form of the hydrolysate may, for example, be obtained by
neutralization of the salt obtained above by alkaline hydrolysis,
with the aid of an organic or inorganic acid (in particular HCl);
in the case of the polysuccinimide derived from aspartic acid, the
hydrolysate thus obtained consists of polyaspartic acid.
"Hydrolysate" is understood according to the invention to refer to
the product obtained by partial or total hydrolysis (by the action
of water) of the polyimide formed; this hydrolysis leads, via
opening of the imide rings, to the formation, on the one hand, of
amide functions and, on the other hand, of carboxylic acid
functions (polypeptidic acids) or carboxylic acid salts
(polypeptidic salts).
The polyimides or their polypeptide hydrolysates prepared according
to the process of the invention may be used in particular in the
field of detergents.
The subject of the present invention is thus also a detergent
composition containing a polyimide such as obtained according to
the abovedescribed process, which polyimide is capable of
generating by hydrolysis in the detergent medium a polypeptide
"builder" which is at least 80%, preferably at least 85%,
biodegradable, or a hydrolysate of the said polyimide, which
hydrolysate takes the form of a polypeptidic acid or salt which is
at least 80%, preferably at least 85%, biodegradable.
"Builder" is understood to refer to any constituent which improves
the performance of the surface agents of a detergent composition. A
"builder" generally possesses a multitude of functions:
in a detergent medium it ensures that undesirable ions are removed,
especially alkaline-earth metal ions (calcium and magnesium), by
sequestration, complexation or precipitation in order to prevent
the precipitation of the anionic surfactants,
it provides a reserve of alkalinity and of ionic strength,
it maintains the extracted dirt in suspension,
it prevents the washing from being encrusted with minerals.
Detergent compositions containing a polyimide obtained in
particular by polycondensation of aspartic acid, which is capable
of generating a polypeptide "builder" by hydrolysis in the
detergent medium, or containing a polypeptide poly(amino acid)
"builder", are already known (EP-A-511 037 and EP-A-454 126). It
has been observed that the polysuccinimide hydrolysates obtained by
polycondensation of aspartic acid, used in these compositions, have
a biodegradability in natural medium which generally does not
exceed 75% (EP-A-511 037).
The detergent compositions according to the invention have
excellent primary and secondary detergent properties.
Detergent composition according to the invention denotes laundry
washing products, dishwasher cleaning products or any other washing
product for domestic use.
"Detergent bath" or "detergent medium" is understood to refer to
the aqueous solution of the washing product (detergent composition)
present in the washing machine in the course of the washing cycles;
the amount of washing product present is that recommended by the
manufacturer; this is generally less than 20 g/liter; the pH of
such a solution is greater than 9.
The invention relates to a detergent composition containing a
polyimide which has a charge density COO.sup.- which my range from
0 to 5.times.10.sup.-4 mol/g of polymer and which is capable of
acquiring in the detergent bath a charge density COO.sup.- at least
equal to 10.sup.-3 mol/g of polymer or a hydrolysate of the said
polyimide, which polyimide is derived from the thermal
polycondensation of at least one amino acid, optionally followed by
hydrolysis, the said composition being characterized in that the
said polyimide is obtained by thermal polycondensation of at least
one amino acid carried out in the presence of at least one "acid
catalyst" chosen from
sulphuric, nitric, phosphorous, sulphurous, hydrofluoric, silicic
and sulphonic acids, organic sulphonic acids containing less than
50 carbon atoms, preferably less than 25 carbon atoms, amino acids
bearing a non-carboxyl strong acid function, organic phosphonic
acids, organic carboxylic acids having a pK.sub.a lower than or
equal to 5, preferably lower than or equal to 3;
precursors of these acids;
salts of these acids and of an amino acid which is similar to or
different from that or those used;
salts of these acids and of a polyimide derived from the
polycondensation of at least one amino acid which is similar to or
different from that or those used;
hydrochloric acid and its precursors
salts of hydrochloric acid and of an amino acid which is similar to
or different from that or those used, when the amino acid to be
polycondensed is other than glutamic acid;
salts of hydrochloric acid and of a polyimide derived from the
polycondensation of at least one amino acid which is similar to or
different from that or those used;
acid salts of sulphuric, phosphoric or phosphorous acids or their
precursors;
phosphoric acid precursors other than phosphoric anhydride or
polyphosphoric acids;
and Lewis acids;
according to an "acid catalyst"/amino acid molar ratio of at least
0.001, preferably of the order of 0.005 to 10 and very particularly
of the order of 0.01 to 5.
The nature of the amino acids, of the examples of "acid catalysts"
and the operating conditions of the polycondensation operation
which may be used have already been mentioned hereinabove.
The polyimides or their hydrolysates entering into the composition
of the invention may have a weight-average molecular mass of the
order of 2000 to 10.sup.7 and generally of the order of 3500 to
60000.
The amount of polyimide or hydrolysate of the said polyimide
entering into the detergent composition which forms the subject of
the invention may range from 0.2 to 80%, preferably from 2 to 10%,
by weight of the said detergent composition.
In addition to this polyimide or polyimide hydrolysate, at least
one surface-active agent is present in the detergent composition in
an amount which may range from 2 to 50%, preferably from 6 to 30%,
by weight of the said detergent composition.
Among the surface-active agents entering into the detergent
composition which forms the subject of the invention, there may be
mentioned:
anionic surface-active agents of the soap type and alkali metal
type (alkali metal salts of C.sub.8 -C.sub.24 fatty acids), alkali
metal sulphonate type (C.sub.8 -C.sub.13 alkylbenzenesulphonates,
C.sub.12 -C.sub.16 alkylsulphonates, sulphated C.sub.6 -C.sub.16
fatty alcohols, sulphated C.sub.8 -C.sub.13 alkylphenols), alkali
metal sulphosuccinate type (C.sub.12 -C.sub.16 alkyl
sulphosuccinates), etc.
nonionic surface-active agents of the polyoxyethylenated C.sub.6
-C.sub.12 alkylphenol, oxyethylenated C.sub.8 -C.sub.22 aliphatic
alcohol, ethylene oxide/propylene Oxide block copolymer or
optionally polyoxyethylenated carboxylic amide type, etc.
Amphoteric surface-active agents of the alkyldimethylbetaine type,
etc.
Cationic surface-active agents of the alkyltrimethylammonium or
alkyldimethylammonium bromide or chloride type, etc.
Various constituents may in addition be present in the detergent
composition of the invention in order to obtain washing products or
cleaning products in powder form.
Thus, there may in addition be present in the detergent composition
described above:
"builders" of the type:
phosphates in an amount of less than 25% of the total formulation
weight,
zeolites up to approximately 40% of the total formulation
weight,
sodium carbonate up to approximately 80% of the total formulation
weight,
silicates or cogranulates of sodium silicate and sodium carbonate
up to approximately 40% of the total formulation weight,
nitriloacetic acid up to approximately 10% of the total formulation
weight,
citric acid or tartaric acid up to approximately 20% of the total
formulation weight, the total mount of "builder" corresponding to
approximately 0.2 to 80%, preferably from 20 to 45%, of the total
weight of the said detergent composition,
bleaching agents of the perborate, chloroisocyanate or
N,N,N',N'-tetraacetylethylenediamine (TAED) take up to
approximately 30% of the total weight of the said detergent
composition,
anti-redeposition agents of the carboxymethyl cellulose or methyl
cellulose type, or of the polyethylene
terephthalate/polyoxyethylene terephthalate copolymer type having a
polyethylene terephthalate/polyoxyethylene terephthalate molar
ratio of 25/75 to 90/10, preferably from 50/50 to 90/10, derived
from polyethylene glycol having a molar mass of the order of 600 to
5000, in amounts which may range up to approximately 5% of the
total weight of the said detergent composition,
anti-encrustation agents of the acrylic acid and maleic anhydride
copolymer type in an amount which may range up to approximately 10%
of the total weight of the said detergent composition,
fillers of the sodium sulphate type in an amount which my range up
to 50% of the total weight of the said detergent composition.
The detergent composition which forms the subject of the invention
is effective either as a primary detergent or as a secondary
detergent.
In addition, incorporation of the polyimide thus prepared or its
hydrolysate guarantees that the detergent composition claimed has
total (at least 80%, preferably at least 85%) and easy
biodegradability when this compound leaves the washing machine, and
when discharged into a natural environment.
The examples which follow are given as a guide and cannot be
considered as limiting the scope and spirit of the invention.
The viscosity index (VI) given in these examples is measured using
a SCHOTT AVS 350 capillary viscosimeter from an amount of
polysuccinimide (PSI) dissolved in 0.5N sodium hydroxide so as to
give a concentration of 0.002 g/ml at a temperature of 25.degree.
C.
In these examples the biodegradability of the hydrolysates is
measured according to AFNOR standard T90-312 (in accordance with
ISO international standard 7827 of Oct. 15, 1984).
The test is carried out using:
an inoculum obtained by filtration of the inlet water of the
municipal plant at Saint Gemin au Mont d'Or (Rhone), as it is or
after adaptation
a test medium containing 4.times.10.sup.5 bacteria/ml
an amount of product to be tested such that the test medium
contains an organic carbon concentration of the order of 40
ml/g.
The biodegradation rate is measured as a function of the time under
the conditions of discharge into river water.
For this measurement the samples tested were obtained by hydrolysis
by a dilute sodium hydroxide solution of the polysuccinimides
prepared, until a sodium polyaspartate solution at a concentration
of approximately 6% and of pH of the order of 9 to 11 is
obtained.
The level of biodegradability is characterized by the following two
parameters:
the maximum rate of biodegradation (MRB)
the time needed to pass from a biodegradation rate of 10% to a rate
of 90% of the maximum rate of biodegradation (t 10-90).
Measurement of the coloration according to the HUNTER Lab
method
The coloration of the polysuccinimide powders or of their
hydrolysates is determined by measurement on an ACS SPECTRO-SENSOR
II.RTM. spectrocolorimeter.
Measurement conditions:
illuminant: D 65
observation angle: 2.degree.
The 3 values measured are
L: Luminance which varies between 0 (black) and 100 (white)
a: Coloration red (a positive)/green (a negative)
b: Coloration yellow (b positive)/blue (b negative)
These values are calculated from the measurements according to the
formulae ##EQU1## X, Y, Z: tristimulus values corresponding to the
3 primary colours obtained with the sample; Xo, Yo, Zo: tristimulus
values for the perfect diffuser of the source used; Ka, Kb:
coefficients of the source used.
Preparation of the acid salts of aspartic acid
The acid salts of aspartic acid used in the examples which follow
are prepared from the following starting materials
______________________________________ AA Acid Solvent mol nature
mol nature ml ______________________________________ 0.225 95%
H.sub.2 SO.sub.4 0.52 EtOAc 100 0.225 CH.sub.3 SO.sub.3 H 0.23
H.sub.2 O 100 0.225 96% PTSA.H.sub.2 O 0.225 H.sub.2 O 100 0.3765 4
N HCl 89 ml -- -- ______________________________________
The above abbreviations have the following meaning AA: L-aspartic
acid (Chemie Linz) PTSA: para-toluenesulphonic acid The aspartic
acid sulphate (insoluble in ethyl acetate) obtained is separated
off by filtration, followed by drying under vacuum. The aspartic
acid sulphonates (water-soluble) obtained are separated off by
evaporation under vacuum, followed by drying under vacuum. The
aspartic acid hydrochloride obtained is separated off by
freeze-drying.
EXAMPLE 1
Into a 100-ml rotary evaporator flask are introduced
5 g of L-aspartic acid from Chemie Linz (equivalent to
3.76.times.10.sup.-2 mol)
0.360 g of methanesulphonic acid (equivalent to
3.76.times.10.sup.-3 mol)
25 ml of dibutyl phthalate
The reactants are heated to 180.degree. C. (temperature of the oil
bath) under water-pump vacuum, according to the following
temperature profile:
temperature rise from 25.degree. C. to 180.degree. C. over 45
min
temperature maintained for 1 h 20 min at 180.degree. C. (at 12000
Pa).
The suspension obtained is filtered; the product is ground and
first washed with ether, and then with the aid of 5.times.100 ml of
water.
A cream-coloured powder is obtained which is dried under vacuum
over P.sub.2 O.sub.5.
2.26 g of PSI is recovered (equivalent to a yield of 62%).
The product has a viscosity index equal to 7.81 ml/g.
This polysuccinimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 98%
t 10-90: 13 days
EXAMPLE 2
20.32 g of L-aspartic acid hydrochloride are introduced into a
250-ml rotary evaporator flask. The reactor is placed under inert
atmosphere using nitrogen and then gradually heated from room
temperature to the temperature of 240.degree. C., according to the
following temperature profile (temperature of the oil bath):
1.5.degree. C./minute from 20.degree. C. to 150.degree. C.
temperature maintained for 1 hour at 150.degree. C.
then 2.degree. C./minute up to 240.degree. C.
finally, temperature maintained for 30 minutes at 240.degree.
C.
The reaction mass is allowed to cool to room temperature.
11.92 g of PSI are obtained.
The product has a viscosity index equal to 10.50 ml/g and a HUNTER
coloration
L=85.6
a=1.46
b=19.67
This polysuccinimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 91%
t 10-90: 8 days
EXAMPLES 3-18
Into an unsealed SCHOTT.RTM. tube (screw reactor) are
introduced
5 g of L-aspartic acid (Chemie Linz)
0.5 g of "acid catalyst" featured in Table 1
The reactants are heated to 200.degree. C. according to the
following temperature profile:
temperature rise from 25.degree. C. to 200.degree. C. over 20
min
temperature maintained for 4 h at 200.degree. C.
The product is poured into 1 liter of water, filtered off and then
dried under vacuum in a desiccator at 40.degree. C.
EXAMPLES 19-28
The operation described in Examples 3-18 is repeated, varying the
amounts of "acid catalyst" and the duration of the fixed
temperature period according to the characteristics given in Table
2.
EXAMPLE 29
Into a 100-ml rotary evaporator flask are introduced
5 g of L-aspartic acid from Chemie Linz (equivalent to
3.76.times.10.sup.-2 mol)
5 g of aspartic acid hydrochloride (equivalent to 3.times.10.sup.-2
mol)
followed, after mixing of the powders, by 50 ml of decalin
The reactants are heated to 200.degree. C. (temperature of the oil
bath) at atmospheric pressure according to the following
temperature profile:
temperature rise from 25.degree. C. to 200.degree. C. over 10
min
temperature maintained for 4 hours at 200.degree. C.
The suspension obtained is filtered; the product is rinsed with
decalin and washed with the aid of 2.times.50 ml of ether.
A light yellow powder is obtained which is dried in a heated
desiccator.
7.2 g of PSI are recovered (equivalent to a yield of 100%).
The product has a viscosity index equal to 7.35 ml/g and a HUNTER
coloration
n=90.4
a=-1.6
b=16.4
EXAMPLE 30
Into a 2-liter reactor with an anchor stirrer are introduced
500 g of L-aspartic acid
55.5 g of KHSO.sub.4
The polycondensation operation is carried out at atmospheric
pressure for 7 hours at a bath temperature of 200.degree. C.
The product obtained is washed with 6.times.6 liters of water and
then dried under vacuum (44 h at 6000 Pa at 70.degree. C.).
310 g of PSI are recovered, which corresponds to a yield of
85%.
The product has a viscosity index VI=10.89 ml/g and a HUNTER
coloration
L=92.1
a=1.0
b=8.8
This polysuccinimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 90%
t 10-90: 7 days
EXAMPLE 31
Into a 250-ml rotary evaporator flask are introduced
50.0 g of L-aspartic acid
5.94 g of NaHSO.sub.4.H.sub.2 O
The polycondensation operation is carried out at atmospheric
pressure for 5 h at a bath temperature of 200.degree. C.
The product obtained is washed with 2.times.4 liters of water and
then dried under vacuum (16 h at 6000 Pa at 90.degree. C.).
27.4 g of PSI are recovered, which corresponds to a yield of
75%.
The product has a viscosity index VI=9.78 ml/g and a HUNTER
coloration
L=93.1
a=1.0
b=7.4
This polysuccimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 85%
t 10-90 : 5 days
EXAMPLE 32
Into a 250-ml rotary evaporator flask are introduced
50.0 g of L-aspartic acid
5.56 g of KHSO.sub.4
The polycondensation operation is carried out under vacuum (6000
Pa) for 5 h at a bath temperature of 200.degree. C.
The product obtained is washed with 3.times.2 l of water and then
dried under vacuum (24 h at 6000 Pa at 90.degree. C.).
25.1 g of PSI are recovered, which corresponds to a yield of
69%.
The product has a viscosity index VI=11.40 ml/g and a HUNTER
coloration
L=89.8
a=1.3
b=10.9
EXAMPLE 33
Into a 250-ml round-bottomed flask fitted with a paddle mixer are
introduced 33.3 g of L-aspartic acid (Chemie Linz).
Heating is carried out at 190.degree. C. with stirring, with
introduction of gaseous HCl at a flow rate of 25 liters/h; the
introduction lasts 15 min.
Period of heating (including that for the introduction of HCl):
2 h at 190.degree. C.
followed by 2 h 30 at 200.degree. C.
The powder obtained is ground in a mortar and then washed with
water and dried.
The yield of PSI is 100%.
The product has a viscosity index equal to 7.79 ml/g.
This polysuccinimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 97%
t 10-90: 4 days
EXAMPLES 34-36
The operation described in Examples 19-28 is repeated, using
5 g of aspartic acid (Chemie Linz)
10 mol % of 95% H.sub.2 SO.sub.4
at various temperatures (Table 3), with maintenance of the
temperature for 4 h.
The product is washed with the aid of 1 liter of water and dried
under vacuum.
EXAMPLE 37
Into an unsealed SCHOTT.RTM. tube (screw reactor) are
introduced
5 g of L-aspartic acid (Chemie Linz)
2.26.times.10.sup.-3 mol of NaHSO.sub.4.H.sub.2 O
0.5 g of ortho-cresol.
The reactants are heated to 200.degree. C. according to the
following temperature profile:
temperature rise from 25.degree. C. to 200.degree. C. over 20
min
temperature maintained for 4 h at 200.degree. C.
The product is poured into i liter of water, filtered off and then
dried under vacuum in a desiccator at 40.degree. C.
The PSI yield is 82%.
The product has a viscosity index equal to 9.51ml/g.
This polysuccinimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 87%
t 10-90: 7 days
EXAMPLE 38
Into a 250-ml rotary evaporator flask are introduced
26.7 g of L-aspartic acid (Chemie Linz)
2.96 g of KHSO.sub.4.
The flask is immersed for 6 h in a bath preheated to 180.degree.
C.
After washing and drying, a PSI is recovered with a yield of
63.5%.
The product has a viscosity index VI=11.35 ml/g and a HUNTER
coloration
L=92.3
a=0
b=8.3
This polysuccinimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 97%
t 10-90 : 8 days
EXAMPLES 39-41
A mixture is prepared obtained by
incorporating 10 parts by weight of a H.sub.2 SO.sub.4 /K.sub.2
SO.sub.4 mixture according to a ratio given in Table 4 in 90 parts
by weight of L-aspartic acid
then homogenizing the medium by forming a paste using 150 parts by
weight of water and evaporating the water (40.degree. C., 6000 Pa.)
until the water has been completely removed
and grinding.
Approximately 53 g of the powder obtained are introduced into a
250-ml rotary evaporator flask preheated to 200.degree. C.
After polycondensating for 6 h at 200.degree. C., a PSI is
recovered without washing with water, whose characteristics appear
in Table 4.
EXAMPLE 42
A pulverulent medium is prepared by
forming a paste from
50 g of aspartic acid
2.6 g of KHSO.sub.4
using 80 g of water, on an enamelled plate
evaporating the water at 80.degree. C. under vacuum (6000 Pa.)
and grinding using a grinder equipped with blades.
50.6 g of powder are introduced into a 250-ml rotary evaporator
flask.
The polycondensation operation is carried out at atmospheric
pressure for 6 hours at a bath temperature of 200.degree. C. The
medium remains pulverulent throughout the whole of the
polycondensation operation.
42.3 g of product are recovered, which corresponds to a PSI yield
of 63%.
The product has a viscosity index VI=11.3 ml/g and a HUNTER
coloration
L=90.4
a=-2.2
b=9.8
EXAMPLE 43
A pulverulent medium is prepared by
forming a paste from
300 g of aspartic acid
33 g of KHSO.sub.4
using 240 g of water, on an enamelled plate
evaporating the water at 80.degree. C. under vacuum (6000 Pa.)
and grinding using a grinder equipped with blades.
247.6 g of powder are introduced into a 1-liter rotary evaporator
flask.
The polycondensation operation is carried out at atmospheric
pressure for 6 hours at a bath temperature of 200.degree. C. The
medium remains pulverulent throughout the whole of the
polycondensation operation.
The product obtained is washed with 3.times.6 liters of water and
then dried under vacuum (5 h at 6000 Pa and 100.degree. C.).
130.1 g of PSI are recovered, which corresponds to a yield of
80%.
The product has a viscosity index VI=12.0 ml/g and a HUNTER
coloration.
L=94.2
a=-0.3
b=6.5
EXAMPLE 44
A mixture of
300 g of aspartic acid powder
and 33 g of KHSO.sub.4 powder
is subjected to a micronizing operation (cryogenic grinder) until a
particle size of less than 5 .mu.m is obtained.
251.7 g of powder are introduced into a 1-liter rotary evaporator
flask.
The polycondensation operation is carried out at atmospheric
pressure for 6 hours at a bath temperature of 200.degree. C. The
medium remains pulverulent throughout the whole of the
polycondensation operation.
The product obtained is washed with 3.times.6 liters of water and
then dried under vacuum (5 h at 600 Pa and 100.degree. C.).
143.8 g of PSI are recovered, which corresponds to a yield of
87%.
The product has a viscosity index VI=11.1 ml/g and a HUNTER
coloration.
L=95.7
a=-0.6
b=4.2
This polysuccinimide is hydrolysed as indicated above; the
biodegradability of the hydrolysate is the following:
MRB: 95%
t 10-90: 7 days
EXAMPLE 45
In 10 liters of water are dissolved at 90.degree. C.
270 g of aspartic acid
and 30 g of KHSO.sub.4.
The solution obtained is atomized using an ANHYDRO.RTM. spray dryer
(marketed by ANHYDRO).
50.0 g of powder are introduced into a 250-ml rotary evaporator
flask.
The polycondensation operation is carried out at atmospheric
pressure for 6 hours at a bath temperature of 200.degree. C. The
medium remains pulverulent throughout the whole of the
polycondensation operation.
38.6 g of product are recovered, which corresponds to a PSI yield
of 94%.
The product has a viscosity index VI=9.5 ml/g and a HUNTER
coloration.
L=88.6
a=-2.0
b=10.4
EXAMPLE 46
Formulation of a laundry detergent composition using
polysuccinimide obtained in Example 30
By dry-mixing of the various additives the following solid
detergent composition is obtained:
______________________________________ Composition of the washing
product % by weight ______________________________________ Linear
alkylbenzenesulphonate 7.5 CEMULSOL LA 90 .RTM. (polyoxyethylenated
4 lauric acid marketed by RHONE-POULENC) 4 A Zeolite 24 Sodium
silicate (SiO.sub.2 /Na.sub.2 O = 2) 1.5 Sodium carbonate 10 TAED 2
Sodium perborate 15 Ethylenediaminetetraacetic acid 0.1 PSI of
Example 30 3 Tiponal DMSX .RTM. 0.1 Tiponal SOP .RTM. (optical
brighteners 0.1 marketed by CIBA-GEIGY) Siliconated anti-foam 0.2
Alkalase 0.15 Savinase (enzymes) 0.15 Sodium sulphate qs 100%
______________________________________
"Control washing product" will refer to a washing product of the
above composition but containing no PSI.
EXAMPLE 47
The performance of a washing product containing the PSI synthesized
in Example 30 was tested for inorganic anti-encrustation.
This effect was measured after 20 washes carried out in the
presence of the following test cloths:
Testfabric 405 (4) cotton textiles
Krefeld 12A (8) cotton
Inorganic encrustation is calculated from the ash content (in %
relative to the total weight of the cotton) of cloths which are
washed, dried and burned at 950.degree. C. for 3 hours. The
encrustation inhibitory effect is assessed by the ash content with
additives/ash content without additives ratio featured under the
letter T. The results are the following.
______________________________________ T % on T % on
______________________________________ Testfabric 405 Krefeld 12A
28 58 ______________________________________
EXAMPLE 48
This example demonstrates the calcium ion sequestering capacity of
the PSI of Example 30 after in situ hydrolysis.
The calcium ion sequestering capacity is measured with the aid of
an electrode having a selective membrane which is permeable to
calcium ions.
A calibration curve is first plotted using 100 ml of an NaCl
solution at a concentration of 3 g/l of pH 10.5 to which quantities
of calcium ions varying from 10.sup.-5 to 3.times.10.sup.-3 mol/l
are added and the potential curve delivered by the electrode is
plotted as a function of the free Ca.sup.2+ ion concentration.
The PSI is hydrolysed using concentrated sodium hydroxide solution
until a sodium polyaspartate solution at a concentration of 20% by
weight and of pH =10.5 is obtained. The solution obtained is called
the "hydrolysate".
This solution is diluted until 100 g of aqueous polyaspartate
solution of concentration equivalent to 10 g/l of PSI are obtained;
the pH is adjusted to 10.5 using concentrated sodium hydroxide
solution. 0.3 g of NaCl powder is added.
The straight line free [Ca.sup.2+ ]/bound [Ca.sup.2+
]=f(free[Ca.sup.2+ ]) is plotted.
From this straight line are determined:
the complexation constant K of the calcium ions of the polymer
the number So of complexation sites of the polymer, defined by
##EQU2##
According to this evaluation method the polyaspartate obtained by
hydrolysis of the PSI of Example 30 has the following
characteristics:
______________________________________ So (sites/g or polymer) Log
K ______________________________________ 3.6 .times. 10.sup.-3 3.4
______________________________________
EXAMPLE 49
This example demonstrates the capacity of the PSI of Example 30 to
disperse calcium carbonate after in situ hydrolysis.
In a 100 cm.sup.3 test tube (height 26 cm; diameter 3 cm), 2 g of
precipitated calcium carbonate are dispersed in 100 ml of an
aqueous solution of pH 10.5 (NaOH) containing 3 g/l of NaCl,
3.times.10.sup.-3 mol/l of CaCl.sub.2 and the hydrolysate as
prepared in the preceding example, at various concentrations.
The level of the sediment is measured in cm.sup.3 at the end of 10
min and the curve of the level of sediment is plotted as a function
of the concentration in ppm of the polymer (expressed as dry
material).
The curve in FIG. 1 first of all shows a flocculation phenomenon
(too low a degree of covering of the polymer particles) followed by
restabilization.
This capacity to stabilize inorganic particles is particularly
advantageous since it is known that the latter are the cause of
encrustration phenomena due to the deposits which accumulate on the
cotton.
TABLE 1 ______________________________________ Biode- gradbility t
10- YR VI Colour MRB 90 Ex Caltalyst (%) (ml/g) L a b (%) (d)
______________________________________ 3 H.sub.3 PO.sub.3 99 19.04
88.8 -1.9 11.2 88 12 4 NaHSO.sub.4.H.sub.2 O 89.5 9.79 5 CH.sub.3
SO.sub.3 H 85 13.92 82.1 1.3 15.8 6 95% H.sub.2 SO.sub.4 88 10.36
55.8 2.7 8.2 93 8 7 PTSA 91 13.03 73.2 2.7 13.8 90 26 8 KHSO.sub.4
80 9.98 88.1 2.1 11.7 90 28 9 NaH.sub.2 PO.sub.4 61 8.64 89.8 2.4
10.2 10 salicylic 100 8.08 84.0 2.2 12.2 81 15 acid 11 AlCl.sub.3
95 7.68 88.8 -0.4 15.2 12 ZnCl.sub.2 71 8.48 88.2 1.3 13.2 13
AA/H.sub.2 SO.sub.4 * 99.9 9.71 81.0 2.2 14.7 14 AA/PTSA* 82.3
10.49 83.1 2.3 13.5 15 AA/CH.sub.3 SO.sub.3 H* 86 10.3 88.4 1.3
13.1 16 sulphobenzoic 85.4 9.02 87 7 acid 17 cyanuric 93 8.88 90 7
chloride 18 ethylphos- 100 10.97 92 7 phonic acid
______________________________________ *Aspartic acid salts YR:
yield of PSI recovered
TABLE 2
__________________________________________________________________________
Biodegradability AA Catalyst Duration YR VI Colour MRB t 10-90 Ex
(g) nature g (h) (%) (ml/g) L a b (%) (d)
__________________________________________________________________________
19 5 95% H.sub.2 SO.sub.4 0.058 4 71 9.14 84.6 3.0 12.3 83 7 20 5
95% H.sub.2 SO.sub.4 0.116 4 85 9.76 87.8 2.6 11.0 21 5 95% H.sub.2
SO.sub.4 0.387 1 65 7.90 22 5 95% H.sub.2 SO.sub.4 0.387 2 90 7.97
23 5 95% H.sub.2 SO.sub.4 0.387 3 92 8.76 66.7 3.1 12.2 24 5 95%
H.sub.2 SO.sub.4 0.387 4 94 9.04 25 5 95% H.sub.2 SO.sub.4 0.387 5
97 9.13 26 5 95% H.sub.2 SO.sub.4 0.387 8 98 9.45 61.3 4.1 13.1 27
5 NaHSO.sub.4.H.sub.2 O 0.155 4 68.2 8.73 80 11 28 5
NaHSO.sub.4.H.sub.2 O 0.311 4 76.4 9.40 87.9 1.8 11.4
__________________________________________________________________________
TABLE 3 ______________________________________ T YR VI Colour Ex
.degree.C. (%) (ml/g) L a b ______________________________________
34 165 64 7.22 92.0 -0.2 6.6 35 165 81 8.27 78.4 2.0 11.6 36 220 95
9.77 68.4 3.8 15.2 ______________________________________
TABLE 4 ______________________________________ H.sub.2 SO.sub.4 /
Med- Development K.sub.2 SO.sub.4 ium of the YR VI Colour Ex
(molar) (g) medium (%) (ml/g) L a b
______________________________________ 39 1 53.2 powder 86 11.40
91.9 0.6 9.3 40 3 53.2 friable 93 9.48 90.1 -0.3 10.9 medium 41 2
53.4 friable 90 11.00 91.1 -0.2 9.5 medium
______________________________________
* * * * *